METHODS OF PHOTOPROTECTING A MATERIAL AGAINST SOLAR UV
RADIATION USING PHOTONIC PARTICLES; COMPOSITIONS
The invention relates to methods of photoprotecting
various materials using a dispersion of photonic
particles, and also to compositions and methods of
treating human keratinous materials.
Prior art
Current photoprotective compositions use
combinations of various screening agents, especially
soluble or insoluble organic screens. The absorption
spectrum of each of said screens is rarely broad enough
to cover the whole UV spectrum, and combinations are
necessary.
Further, a large number of soluble organic screens
may cause compatibility problems with the ingredients
usually contained in them, especially as a result of
interactions with other organic screens or with active
molecules such as antioxidants or vitamins, and their
photostability may not be entirely satisfactory. Many
patents are concerned with solving this problem,
indicating that this problem is recurrent.
Many non-cosmetic industry sectors also use UV
screens to photoprotect various materials against the
effects of UV radiation, in particular solar radiation.
This applies in particular with pair.t, ink, or
protective coating formulations for applying to
substances that are permanently exposed to UV radiation,
such as building materials, materials used in the
automobile industry, or plastic packaging materials. In
particular, UV screens are being developed for colorant
formulations, which screens need to be transparent,
photostable, compatible with the usual ingredients
contained in said formulations, and effective in
providing the color with the desired resistance to light.
This also applies with polymer compositions used in
particular in the manufacture of plastics materials that
are stable in storage; they need the development of UV
light screens that are particularly adapted to methods of
manufacturing and transforming polymers, and in
particular they have to be able to tolerate the high
temperatures used in extrusion.
In the natural fiber and/or artificial fiber and/or
synthetic fiber industry, broad spectrum photostable UV
screens are being developed that are compatible with
methods of manufacturing said fibers, in particular in
the context of the manufacture of polyamide fibers such
as nylon, which filters are resistant to high
temperatures and enable UV protection to be incorporated
during" extrusion. Further, UV screens are being
developed that have good affinity, good adhesion to
fibers, and thus in particular that provide good
resistance to frequent washing. The UV screens being
developed must also provide both good protection of the
textile fibers and also of the skin and other human
keratinous material in contact with said fibers.
The mineral or organic glass industry, in particular
glass used in ophthalmology, is developing UV screens
that are to have a broad spectrum (active in the UVA and
in the UVB regions),.and that are photostable,
transparent, and compatible with the various techniques
for treating glass such as methods of keying onto the
glass matrix or applying a photoprotective coating, for
example with polycarbonate glass.
Application WO 06/136724 shows that it is known to
use monodisperse particles that are capable of forming a
lattice and that have optical screening properties in the
UVB, UVA and infrared. In that application, the
particles have to become organized on the skin.
In the publication by J. Wang, Polym Int 57:509 -
514, 2008, the authors produced monodisperse PMMA
spheres with various diameters (95 nm, 114 ran, 134 nm,
142 nm and 150 nm). Each diameter corresponded to a
reflection maximum (250 nm, 280 nm, 330 nm, 350 nm,
380 nm) when the particles are organized into a lattice.
Application WO 08/007267 describes the use of hollow
particles that are capable of becoming organized into a
photonic crystal for makeup and UV photoprotection
applications.
Patent OS 6 894 086 describes various photonic
particles, especially colored, or reflecting
electromagnetic radiation outside the visible spectrum.
Applications US 2003/0116062 and US 2006/0002875
describe photonic particles, but do not use them in a
method of photoprotection against solar ultraviolet
radiation.
The publication by A. Stein (Chem Mater 2002, 14,
3305 - 3315) discloses photonic particles having a
reflection band in the long UVA spectrum (374 nm).
The publication by E. Thomas (Nat Mat Vol 6, 957 -
960, 2008) discloses a gel having a reflection spectrum
including a plurality of reflection peaks of distinct
order.
There is a need to benefit from non-soluble
screening materials that can be used to cover the UVA
and/or DVB spectrum, that are completely harmless, inert
towards the environment, photostable, and not
photoreactive, and that do not have compatibility
problems with the other constituents of the compositions
containing them, do not modify the mechanical properties
of the materials of the packaging in a negative manner,
and do not release nanoparticles, and that are
transparent to visible light.
There is also a need to develop novel materials that
screen UV radiation and that are adapted to
photoprotecting industrial materials such as those
mentioned above.
The invention aims to achieve all or some of these
objects.
In first exemplary embodiments, the invention
provides a method of photoprotecting a material against
solar UV radiation, comprising treating said material by
means of a composition comprising a dispersion of
photonic particles with a mean size in the range 1 µm
[micrometer] to 500 µn, each- comprising a diffracting
arrangement of monodisperse nanoparticles or voids, the
diffraction spectrum of said arrangement including a
first order reflection peak in the wavelength range
250 nm [nanometer] to 400 nm, or comprising integrating
said dispersion of photonic particles into said material.
In second exemplary embodiments, the invention
provides a non-therapeutic, and in particular cosmetic,
method of photoprotecting human keratinous material
against solar UV radiation, comprising applying a
cosmetic composition comprising a dispersion of photonic
particles with a mean size in the range 1 µm to 500 µm,
each comprising a diffracting arrangement of monodisperse
nanoparticles or voids, the diffraction spectrum of said
arrangement including a first order reflection peak in
the wavelength range 250 nm to 400 nm.
In the context of the invention, the term
"diffracting arrangement" means a set of particles or
voids diffracting incident light in a manner that screens
UV and/or produces coloration and/or modifies the
spectral reflectance, depending on the application.
The presence of a first order reflection peak in the
wavelength range 250 nm to 400 nm means that the
arrangement diffracts light of at least one wavelength in
the range 250 nm to 400 nm with an interference order
equal to 1, thereby at-least partially reflecting it.
Such a first order reflection peak in the UV implies
that, the reflection peaks of the following orders are
located at shorter wavelengths, and thus outside the
visible region. This renders the arrangement colorless
and facilitates the production of a composition that is
colorless, which is preferable in the context of a
sunscreen application.
By way of example, the composition used in the
photoprotection method in accordance with the invention
has an SPF index of at least 10, preferably 15, more
preferably at least 30, 45 or 60. The SPF index
(Sunscreen Protection Factor) is defined in the article
"A new substrate to measure sunscreen protection factors
throughout the ultraviolet spectrum", J. Soc. Cosmet.
Chem., 40, 127 - 133 (May/June 1989).
The formulation of the composition is, for example,
selected such that the composition has a transmission
factor of 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5% or less,
or preferably of 1% or less, for at least one wavelength
in the range 250 nm to 400 nm, preferably over the whole
of said range. Screening is much better when the
transmission factor is low in the range 250 nm to 400 nm.
In accordance with other exemplary embodiments, the
invention provides a photoprotective composition for
carrying out the photoprotection method of the invention.
Such a composition has any of the above characteristics.
In accordance with other exemplary embodiments, the
invention provides a method of preparing a cosmetic-
composition, comprising dispersing the photonic particles
of the invention in a cosmetically acceptable medium.
Other exemplary embodiments of the invention provide
a composition for use in a method of photoprotection of
human keratinous material against solar UV radiation, in
particular in a method for reducing the risk of
apparition of a skin career,
wherein said composition comprises a dispersion of
photonic particles with a mean size in the range 1 µm to
SCO µm, each comprising a diffracting arrangement of
monodisperse nanoparticles or voids, the diffraction
spectrum of said arrangement including a first order
reflection peak in the wavelength range 250 nm to 400 nm.
This composition may present, unless the contrary is
specified, all the properties of the cosmetic
compositions of the invention described below.
In accordance with other exemplary embodiments, the
invention provides a photonic particle with a mean size
in. the range 1 µm [micrometer] to 500 urn, especially in
the range 1 pm to 300 pm, comprising a diffracting
arrangement of hollow nanoparticles.
In other exemplary embodiments, the invention
provides:
• a non-therapeutic, and in particular cosmetic,
method of photoprotecting human keratinous material
against solar UV radiation;
• a method of coloring and/or lightening human
keratinous material;
• a method of modifying the spectral reflectance of
human keratinous material;
each of said methods comprising applying a cosmetic
composition comprising a dispersion of photonic particles
with a mean size in the range 1 µm to 500 µm, especially
in the range 1 µm to 300 µm, each of said photonic
particles comprising a diffracting arrangement of hollow
nanoparticles.
Other exemplary embodiments of the invention also
provide a phoronic particle for use in a method of
photoprotection of human keratinous material against
solar "JV radiation, in particular in. a method for
reducing the risk of apparition of a skin cancer,
wherein the photonic particle has a mean size in the
range 1 µm to 500 pm, especially in the range 1 µm to
300 µm, and. comprises a diffracting arrangement of hollow
nanoparticles.
Other exemplary embodiments of the invention provide
a composition for use in a method of photoprotection of
human keratinous material against solar UV radiation, in
particular in a method for reducing the risk of
apparition of a skin cancer,
wherein the composition comprises a dispersion of
photonic particles with a mean size in the range 1µm to
500µm, especially in the range lµm to 300pm, and
comprises a diffracting arrangement of hollow
nanoparticles. Other exemplary embodiments of the
invention provide a.composition, in particular a cosmetic
composition, comprising a dispersion of photonic
particles each having a form factor of less than 2, said
particles comprising a diffracting arrangement of voids
or monodisperse nanoparticles in a thermo-, electro- or
photocrosslinkable matrix.
In accordance with further exemplary embodiments the
invention provides:
. a non-therapeutic, and in particular cosmetic,
method of photoprotecting human keratinous material
against solar UV radiation;
• a method of coloring and/or lightening human
keratinous material;
• a method of modifying the spectral reflectance of
human keratinous material;
each of said methods comprising applying to said
keratinous material a cosmetic composition comprising a
dispersion of photonic particles each having a form
factor of less than 2, said particles comprising a
diffracting arrangement of voids or monodisperse
nanoparticles in a thermo-, electro- or
photocrosslinkable matrix.
Other exemplary embodiments cf the invention provide
a composition for use in a method of photoprctecticn of
human keratinous material against solar UV radiation, in
particular in a method for reducing the risk of
apparition of a skin cancer,
wherein said composition comprises a dispersion of
photonic particles each having a form factor of less than
2, said particles comprising a diffracting arrangement of
voids or monodisperse nanoparticles in a thermo-,
electro- or photocrosslinkable matrix.
In other exemplary embodiments, the invention
provides:
• a method of photoprotecting an ink, a paint, or a
coating, comprising incorporating at least one
composition comprising a dispersion of photonic particles
as defined above into said ink or paint or said coating;
• a method of photoprotecting a material
manufactured from at least one synthetic or natural
polymer, comprising treating said polymer with a
composition comprising a dispersion of photonic particles
as defined above or comprising integrating at least said
composition into said material;
• a method of photoprotecting an organic or mineral
glass, comprising treating said glass with at least one
composition comprising a dispersion of photonic particles
as defined above or comprising integrating at least said
composition into said glass;
• a method of photoprotecting a material comprising
at least natural fibers and/or artificial fibers and/or
synthetic fibers such as textiles or papers, comprising
treating said material with at least one composition
comprising a dispersion of photonic particles as defined
above or comprising integrating at least said composition
into said material.-
The polymeric materials of the invention are, in
particular plastic materials that are capable of being
molded or worked, in general hor and under pressure, in
order to result in a semimanufactured product or an
article.
The polymers used for said materials are preferably
selected from three major categories:
(i) thermoplastics such as, for example:
• acrylonitrile-butadiene-styrene (ABS) copolymers;
• cellulose acetate (CA) polymers;
• expanded polystyrenes (EPS);
• polystyrenes (PS);
• polyamides (FA);
• polybutylene terephthalate (PBT);
• polyethylene terephthalate (PET);
• polycarbonates (PC) ;
• polyethylenes (PE) ;
• polypropylenes (PP) ;
• polymethyl methacrylate (PMMA);
• polyformaldehydes (POM);
• polyvinyl acetates (PVAC);
• polyvinyl chlorides (PVC);
• styrene-acrylonitrile (SAN) copolymers;
(ii) thermosets, such as:
• polyepoxides (EP);
• melamine-formaldehyde (MF) copolymers;
• phenol-formaldehyde (PF) copolymers;
• cured polyurethanes(PUR);
• urea-formaldehyde (UF) copolymers;
• unsaturated polyesters,
(iii) technical plastics such as:
• polytetrafluoroethylene (PTFE).
Examples of natural fibers that may be mentioned,
for example, are:
• plant fibers such as cotton, linseed, hemp, jute,
straw, or latex;
• animal fibers such as wool, silk, mohair, angora,
cashmere or alpaca.
Artificial fibers are generally obtained by chemical
treatment (dissolution then precipitation) of natural
substances such as milk caseins for lanital, or cellulose
from various plants (pine bark, bamboo, soya, birch) for
viscose. These chemical treatments are intended to
produce a product that can be spun (capable of passing
through the small holes of a die). At the die outlet,
the filaments obtained are either combined tc form
continuous filaments in the manner of a silk thread, or
are cut into discontinuous fibers in the manner cf wool.
Examples of artificial fibers thai: may, for example,
be mentioned are:
• cellulose acetate;
• cellulose triacetate; and
• viscose.
Particular examples .of textile fibers, are:
• polylactic acid;
• acrylic;
• aramides;
• elasthane: ©Lycra;
• chlorofiber;
• modacrylic;
• polyamide;
• polybenzimidazole;
• polyester;
• polyethylene;
• polyphenolic; and
• polyurea: polyurethane.
Examples of glasses that are suitable for use in the
invention that may be mentioned are conventional mineral
glasses based on silicates, glasses used for optics,
glasses used for ophthalmology, especially organic
glasses such as polycarbonates, for example bisphenol A
polycarbonate or allyl polycarbonate, those used in the
automobile industry (windshields), etc.
Photonic particlss
In the context of the invention, photonic particles
are also known as opals.
The photonic particles may have a form factor of
less than 2, especially less than 1.75. When the
particle is oblong, the form factor denotes the ratio of
its largest longitudinal dimension to its largest
transverse dimension. The photonic particles may be
spherical, then having a form factor of 1.
A form factor of less than 2 may have an advantage
in terms of surface coverage compared with fiat particles
that may become superimposed.
The mean size of the photonic particles may be in
the range 1 urn to 500 urn, for example in the range 1 µm
to 30 0 µm. The term "mean size" denotes the statistical
grain•size dimension at half the population, termed
D(0.5) .
The photonic particles of the invention may comprise
solid or hollow nanoparticles aggregated without a matrix
or dispersed in any type of matrix, for example dispersed
in a thermo-, electro• or photocrosslinkable matrix.
The content by weight of photonic particles may be
in the range 0.1% to 20%, preferably in the range 1% to
10%/ relative to the total composition weight, before
application.
The photonic particles of the invention may,
according to the different embodiments, be categorized as
direct, inverse or pseudo inverse opals, as described
below.
The photonic particles may be colorless.
The photonic particles may be solid or hollow.
Direct opals
Photonic particles of the "direct opal" type employ
an arrangement of solid, optionally composite
nanoparticles.
The photonic particles may comprise nanoparticles
aggregated without a matrix. Such a photonic particle 1
comprising nanoparticles 10 aggregated without a matrix
is shown in Figure 1.
A first method of manufacturing such particles may,
as described in the publication by 5•H Kim et al, JACS,
2006, 123, 10897 - 10904, comprises a step of obtaining a
water-in-oil type emulsion, the aqueous phase comprising
mcnodisperse nanoparticles, followed by a step of
obtaining photonic particles comprising a step of using
microwaves to irradiate the emulsion that has been
obtained.
As described in the publication by S-M Yang,
Langmuir 2005, 21, 10416 - 10421, a second manufacturing
step may comprise a step of aggregating SiO2 or
polystyrene nanoparticles under electrospray.
Photonic particles of the "direct opal" type may
also be obtained by a method such as that described in
the publication "Ordered macroporous titania photonic
balls by micrometer-scale spherical assembly templating"
by Li et al, J. Mater. Chem., 2005, 15, 2551 - 2556.
The photonic particles of the "direct opal" type may
also comprise nanoparticles aggregated in a matrix 20, as
illustrated in Figure 2, which are in contact with one
another, or dispersed in a matrix 20 as shown in
Figure 3.
Several methods in addition to those mentioned above
may be suitable for manufacturing said photonic
particles, especially the method of aggregating SiO2
particles in a silicon matrix as described in Honeywell's
application US 2003/0148088.
As described in the publication by D. Pine, Langmuir
2005, 21, 6669 - 6674, a second method may comprise a
step of aggregation from an emulsion of PMMA
nanoparticles.
The photonic particles of the "direct opal" type may
comprise nanoparticles dispersed in a photo-, electro- or
rhermocrosslinkable matrix.
The advantage of using an organic photo-, electro-
or thermcorcsslinkable, especially phorocrosslinkable or
thermocrosslinkable, matrix is because it is possible to
adjust the distance between the nanoparticles contained
in the matrix in order to vary the optical properties of
the photonic particle. This distance may be a function
of the fraction by weight of the nanoparticles dispersed
in the organic matrix, before photo-, electro- or
thermocrosslinking, especially before photocrosslinking
or thermocrosslinking. Said weight fraction is equal to
the ratio of the weight of nanoparticles divided by the
weight of matrix before thermocrosslinking, electro-
crosslinking or photocrosslinking.
In a preferred implementation of the invention, this
fraction of nanoparticles is. in the range 1% to 90% by
weight, preferably in the range 5% to 60% by weight.
This type of photonic particle may be obtained using
several emulsification methods, for example those
described in the publication by S•H Kim et al, Adv Mater
2008, 9999, 1•7, which employs silica particles
dispersed in a photocrosslinkable ETPTA (ethoxylated
trimethylolpropane triacrylate) resin that can be
photopolymerized under UV, or in the publication "Ordered
macroporous titania photonic balls by micrometer-scale
spherical assembly templating" by Li et al, J. Mater.
Chem., 2005, 15, 2551 • 2556.
In some embodiments, the photonic particles comprise
nanoparticles of polystyrene (FS) aggregated in a silicon
matrix.
In some embodiments, the photonic particles comprise
nanoparticles of polystyrene (PS) dispersed in a thermo-,
electro- or photo-crosslinkable silicone resin.
Inverse opals
Photonic particles of the "inverse cpal" type
comprise holes instead of nanoparticles.
They may be obtained from direct opals after
destroying nanoparticles, for example by calcining or
acid hydrolysis, for example wirh 5% hydrofluoric acid,
therewith leaving empty spaces in the place of ail or
part of the nanoparticles. The destruction step may
possibly cause a reduction in the size of the fingerprint
of the nar.cparticle in the matrix, by up to 50%.
Calcining (500°C or 1000°C) may be carried out on
direct opals based on organic nanoparticles and an
inorganic matrix.
Acid hydrolysis, for example with a hydrofluoric
acid solution, may be carried out on opals based on
inorganic nanoparticles and an organic matrix.
With inverse opals, the ratio of the volume occupied
by the nanoparticles divided by the volume occupied by
the matrix (organic or precursor of the inorganic matrix)
may vary over the range 99/1 to 80/20, thereby having the
effect of causing the surface porosity of the inverse
opals to vary. Such a variation is presented in the
publication by D. Pine, F. Lange, Langmuir 2005, 21,
6669 • 6674.
The inverse opals may be produced using the methods
described above for direct opals comprising nanoparticles
aggregated or dispersed in a matrix, followed by a step
of destroying nanoparticles, for example by calcining or
acid hydrolysis, for example as described in the
following publications:
• A. Stein: Chem. Mater. 2002,14, 3305 - 3315,
wherein opals are produced from monodisperse particles in
zirconium acetate matrixes for ZrO articles, from Ti
propoxide for TiO2 opals, or from tetramethoxysilane
(TMOS) for silica opals. After calcining, the PS
particles give way to voids. The final material is then
milled to produce opal powder;
• D. Pine, F. F. Lange: Langmuir, Vol 21, 15,
2005,6669 - 6674, describing the production of opals in
the form of spheres using a method of emulsification
followed by a step of calcining PMMA particles. The
porosity of the opal is controlled by the ratio: Ti
alkoxides divided by the amount of PMMA particles;
• F. F. Lange, Colloid Polym Sci (2303) 232, 7 • 13,
describing the emulsification of particles of PMKA in the
presence of 'Ti butoxide then calcining the PMMA
particles .
3y their nature, inverse opals are, in the absence
of additional treatment, porous materials having optical
properties that vary as a function of the medium which
can fill the holes in the opals.
In order to guarantee their optical properties in
any medium, photonic particles with an inverse opal
structure may be coated and sealed against the medium
into which they are immersed.
Said coating may, for example, be carried out using
polymers or waxes.
Several methods are possible:
• spray drying: the principle is to dissolve or
disperse (for latexes) the material that is to coat the
photonic particles in a volatile solvent with an
evaporation point of 100oC or less (ethanol, acetone,
isopropanol, water, etc, or mixtures thereof). Spraying
the ensemble into a chamber heated to a temperature that
allows evaporation of the solvent or the mixture results
in the material being deposited to coat the particles.
These are entrained in a stream of air in a container at
ambient temperature, for collection therefrom. An
example that may be mentioned is the publication "Effects
of fabrication conditions on the characteristics of
etamidazole spray dried microspheres": Wang et al, J.
Microencapsulation, 2002, vol.19. No 4, 495 - 510;
• bed of fluidized air: the fluidized air bed method
is a method that is frequently used to dry and
manufacture granules. A temperate stream of air is
introduced via the bottom of a reactor. The suspension,
sprayed by an atomizer into the production chamber, makes
the particles in suspension bigger and they fail to the
bottom whereupon they cannot be lifted by the stream of
air.
In a non-limiting manner, the materials for coating
the particles may be selected from the following:
• waxes and fats with a melting point of mere than
45 °C, especially carnauba wax, beeswax, stearyl stearate,
polyethylene wax, DI 18/22 adipate, pentaerythrityl
tetrastearate, tetracontanyl stearate, or dioctadecyl
carbonate;
• cellulose and cellulose derivatives, in particular
ethylcellulose, hydroxypropyl cellulose,
hydroxypropylmethyl cellulose, hydroxybutyl cellulose, or
polymers sold under the trademark Ethocel®;
• polycaprolactone having a molecular weight in the
range 10000 g/mol [gram/mole] to 80000 g/mol;
• polylactic acid (PLA) and polylactic acid-glycolic
acid (PLAGA) at a ratio lying in the range 90/10 to
50/50;
• polyvinyl alcohol;
• copolymers of polyvinylpyrrolidone and vinyl
acetate; and copolymers of acrylic acid and methyl
metnacrylate sold under the trademark Eudragit© L100.
The weight ratio between the core of the photonic
particle and the shell produced therewith may be in the
range 99.9/0.1 to 80/20, and preferably in the range 99/1
to 90/10.
In exemplary embodiments, the photonic particles
comprising nanoparticles aggregated without a matrix may
optionally be coated by a coating, for example as
described above.
Pseudo-inverse opals
"Pseudo-inverse" type photonic particles comprise
hollow nanoparticles, aggregated without a matrix or
dispersed in any type of matrix, for example dispersed in
a thermc-, electro- or photo-crosslinkable matrix.
Producing direct opals from hollow nanoparticles,
also termed "pseudo-inverse opals", has the advantages of
amplifying the optical effects by a higher index
difference compared with direct opals not using hollow
nanoparticles and of offering a zero porosity compared
with unscoated inverse opals, of optical properties that
are dependent on the medium in which they are dispersed.
The hollow nanoparticles may be as described below.
Janus type photonic particles
The photonic particles may be of the Janus type,
i.e. comprising at least one other diffracting
arrangement of nanoparticles, or even at least two other
diffracting arrangements, the arrangements each having
their own optical properties, especially different
diffraction spectra.
In first exemplary embodiments, one arrangement may
comprise solid nanoparticles and another arrangement may
comprise solid or hollow nanoparticles.
In a variation, one arrangement may comprise hollow
nanoparticles and another arrangement may comprise hollow
nanoparticles.
When the particles comprise a plurality of
arrangements, each arrangement may, for example, cover a
different part of the UV spectrum, in order to obtain
broader photoprotection.
The photonic particles comprising a plurality of
diffracting arrangements may be obtained as taught in the
publication by S-H Kim et al, Adv. Mater. 2008, 9999, 1 -
7 or in the publication "Patterned colloidal photonic
domes and balls derived from viscous photocurable
suspensions" from Kim et al, Adv. Mater. 200B, 20, 3211 •
3217.
When the photonic particles are used at least in
part for their coloring properties, in particular to make
the complexion uniform, the arrangements of
nanoparticles, when illuminated with white light, may
produce different respective colors; the arrangements may
in particular produce a red, green and/or blue color,
thereby enabling a large number of shades to be obtained,
in particular white by additive synthesis of reflected
light.
An arrangement presents a reflected red color, for
example, when the reflectance in the visible spectrum is
at least 50% in the wavelength range 620 r.m to 700 nm,
for an angle of observation in the range 50° to 150°.
For green, the wavelength range under consideration is
490 nm to 550 nm, and for blue, it is 410 nm to 490 nm.
The arrangements may diffract light through the various
respective zones of the photonic particle, for example
two opposed zones, for example two diametrically opposed
hemispherical zones for a photonic particle that is
spherical.
One of the arrangements may have a diffraction
spectrum having at least one first order reflection peak
in the wavelength range 250 nm to 400 nm and another
arrangement may have a diffraction spectrum having at
least one first order reflection peak in the range 250 nm
to 400 nm or in the range 400 nm to 700 nm.
Mixture of photonic particles
The composition of the invention may comprise a
single type of photonic particle or a mixture of at least
two different types of photonic particles, for example
having reflection peaks, especially first order peaks,
centered on different wavelengths located in the visible
or UV region.
The composition may, for example, comprise a mixture
of one type of photonic particles comprising solid
nanoparticles and another type of photonic particles
comprising nanoparticles that may be solid or hollow.
The composition may, for example, comprise a mixture
of one type of photonic particle comprising hollow
nanoparticles and another type of photonic particle
comprising nanoparticles that may be hollow.
The composition may, for example, comprise a mixture
of one type of photonic particle comprising a thermo-,
electro- or photo-crosslinkable matrix and another type
of photonic particle not comprising a thermo•, electro-
or photo-crosslinkable matrix.
Nanoparticles
The photonic particle nanoparticles may have a mean
size in the range 100 nm to 500 nm, preferably in the
range 100 nm to 300 nm. The term "mean size" denotes the
statistical granulometric dimension at half the
population, termed D(0.5).
The nanoparticles may be spherical in shape.
The nanoparticles may be 15% monodisperse or better.
The term "x% monodisperse" as used in the invention means
particles with a mean size having a coefficient of
variation, CV, of x% or less. The coefficient of
variation CV is defined by the relationship CV=sD, s
being the standard deviation of the particle size
distribution and D being the mean size thereof. The mean
size D and the srandard deviation s may be measured for
250 particles by analyzing an image obtained using a
scanning electron microscope, for example that with
reference S•4 500 from the supplier HITACHI. Image
analysis software may be used to facilitate this
measurement, for example Winroof® software, from the
supplier Mitani Corporation. Preferably, the coefficient
of variation of the monodisperse nanoparticles is 10% or
less, more preferably 7% or less, or even more preferably
5% or less, for example substantially of the order of
3.5% or less.
The nanoparticles may be solid or hollow, organic or
inorganic.
The nanoparticles may be monolithic or composite.
When the monodisperse nanoparticles are composites,
they may, for example, comprise a core and a shell
produced from different substances, for example organic
and/or mineral substances.
Inorganic nanoparticles
The nanoparticles may comprise an inorganic
ccnpouno, or even be entirely mineral.
When ~he nanoparticles are inorganic, they may, for
example, comprise at least one oxide/ especially a
metallic oxide, for example selected from silica, oxides
of silica, iron, titanium, aluminum, chromium, zinc,
copper, zirconium and cerium, and mixtures thereof. The
nanoparticles may also include a .metal, especially,
tiranium, silver, gold, aluminum, zinc, iron, copper and
mixtures and alloys thereof.
Organic nanoparticles
The nanoparticles may include an organic compound,
or even be entirely organic.
Materials that may be suitable for producing organic
nanoparticles that may be mentioned are polymers, in
particular with a carbon or silicone chain, for example
polystyrene (PS), polymethyl methacrylate (PMMA) ,
poiyacrylamide (PAM), silicone polymers, NADs ("non
aqueous dispersions") such as rigid NADs for example,
e.g. constituted by 96.7% methyl methacrylate and 3.3%
ethylene glycol dimethacrylate 20% cured in isododecane,
particle diameter: 141 nm (polydispersity Q = 0.14); or
90% methyl methacrylate and 10% allyl merhacrylate,
particle diameter: 170 nm; or 100% methyl dimethacrylate,
particle diameter: 138 nm (polydispersity Q = 0.15); or
poly(methyl methacrylate/ allyl methacrylate), polylactic
acid (PLA), the polylactic acid•glycolic acid (PLA.GA),
celluloses and derivatives thereof, polyurethane,
polycaprolactone, latex form, chitin, or composite chitin
materials.
The glass transition temperature (Tg) of the organic
nanoparticles may be greater than 40°C, and preferably
greater than 60°C.
Hollow nanoparticles
These nanoparticles comprise a core and a shell.
The shell may be organic or inorganic.
The shell of the nanoparticles may, for example, be
formed from PS and the particles may, for example, be
aggregated in an organic matrix.
The shell of the nanoparticles may, for example, be
formed from PS and the particles may, for example, be
dispersed in a thermo•, electro- or photo-crosslinkabie
organic matrix.
The core of said hollow nanoparticles may be
constituted by air or a gas other than air in order to
benefit from a different refractive index, for example
CO•, N2, butane, or isobutane.
The presence of air or another gas inside the hollow
nanoparticles may be used to obtain a large difference in
the refractive index between the nanoparticles and the
surrounding medium, which is favorable in terms of the
intensity of the diffraction peak.
When the nanoparticles are hollow, the difference in
refractive index at a wavelength diffracted between the
core and the shell may be 0.4 or more. Said diffracred
wavelength may be in the range 250 nm to 800 nm, for
example in the range 250 nm to 400 nm. When the
nanoparticles are hollow, the ratio between a largest
dimension of the core and a largest dimension of the
nanoparticle may be in the range 0.5 to 0.8. When the
nanoparticles are hollow, the volume of the core
represents in the range 10% to 80%, preferably in the
range 20% to 60% of the total volume of the nanoparticle.
The thickness of the shell of the hollow
nanoparticles, equal to half the difference between the
largest dimension of the nanoparticle and the largest
dimension of the core of the nanoparticle, may be in the •
range 50 nm to 200 nm, for example in the range 30 nm to
100 nm.
An example of hollow nanoparticles that may be
mentioned are 280 nm nanoparticles from the supplier JSR
SX8 66 (B) .
The core of the nanoparticles may optionally
comprise a sunscreen or a mixture of sunscreens.
Matrix
The photonic particles may comprise hollow or solid
nanoparticles, aggregated or dispersed in.any type of
matrix, for example dispersed in a thermo•, electro- or
photo-crosslinkable matrix, or voids dispersed in any
type of matrix, for example dispersed in a thermo•,
electro- or photo-crosslinkable matrix, as mentioned
above.
The matrix may be organic or inorganic.
Non•limiting examples of organic matrixes that may
be mentioned include acrylic matrixes: polymethyl
methacrylate (PMMA) or polacrylamide (PAM), matrices of
polyethylene terephtalate (PET), polystyrene (PS),
polycaprolactone (PCL), polyvinyl acetate(PVA),
polyvinylethyl acetate (PVEA), and waxes with a melting
point greater than 65°C [celsius], for example greater
than 75°C, and with a hardness of more than 5 KPa and
preferably more than 6 MPa [megapascai].
In particular, the matrix may be thermo•, photo- or
electro-crosslinkable.
The term "photocrosslinkable matrix" means a matrix
in which cross•linking is induced and/or assisted by
light, especially UV.
The term "thermocrosslinkable matrix" means a matrix
in which crosslinking is induced and/or assisted by
adding heat, for example bringing the matrix to a
temperature of more than 60°C.
The term "electrocrosslinkable matrix" means a
matrix in which crosslinking is induced and/or assisted
by applying an electric field.
A matrix may be both thermocrosslinkable and
photocrosslinkable.
The photonic particles may comprise solid or hollow
nanoparticles, dispersed in a thermo•, electro- or photo-
crosslinkable matrix, or voids dispersed in a thermo•,
electro- cr photo-crosslinkable matrix.
The thermocrosslinkable or photocrosslinkable matrix
may be organic.
Non•limiting examples of crosslinkable organic
matrixes that may be mentioned are:
.• photocrosslinkable polymers such as ETPA
{ethoxylated trimethylolpropanetriacrylate), PEGDA
(polyethyleneglycol diacrylate), acrylic resins, PEG
diacrylates, or materials described in FR 2 833 487;
• copolymers, described in FR 2 848 428, which
crosslink by polycycloaddition, of PVA or PVEA and of
styrylpyridiniums with the following formulae:

where R represents a hydrogen atom, an alkyl group or a
hydroxyalkyl group, and R' represents a hydrogen atom or
an alkyl group;
• reactive silicones described in patent FR 2
910 286, i.e. :
* polyorganosiloxanes comprising siloxane units
with formula:
where R is a linear or cyclic monovalent hydrocarbon
group containing 1 to 30 carbon atoms, m is equal to 1 or
2 and R' is an unsaturated aliphatic hydrocarbon group
containing 2 to 10 carbon atoms or an unsaturated cyclic
hydrocarbon group containing 5 to 8 carbon atoms; and/or
• polyorganosiloxanes comprising at least cne
alkylhydrogenosiloxane unit with formula:

where R is a linear or cyclic monovalent hydrocarbon
group containing 1 to 30 carbon atoms or a phenyl group
and p is equal to 1 to 2; and
• thermoplastic, thermocrosslinkable,
electrocrosslinkable polymers.
The matrix, crosslinking may.be chemical
crosslinking, for example using succinimides as described
in application WO 2007/082061 A2 .
For photocrosslinkable matrixes requiring a
photoinitiator, the photoinitiator is selected, for
example, from the following list: DMPA (dimethoxy 2•
phenyl acetophenone), 2•benzyl•2•(dimethylamino)•1•[4• (4•
morphoiino phenyl]•1•butanone sold under the trademark
Irgacure® 369 by Ciba®, 4,4'•bis(diethylamino)benzophenone
sold by Sigma•Aldrich1, 2•hydroxy•4'•(2•hydroxyethoxy)•2•
methylpropiophenone sold by Sigma•Aldrich®, 2•benzyl•2•
(dimethylamino)•4'•morpholinobutyrophenone sold by Sigma•
Aldrich®, phenylbis{2,4, 6•trimethylbenzoyl)•phosphine
oxide sold by Sigma•Aldrich®, isopropyl•thioxanthone sold
by Sigma•Aldrich®, and camphorolactone.
The PEG diacrylates may, for example, be crosslinked
using a photoinitiator such as camphorolactone.
Examples of inorganic matrixes that may be mentioned
are metallic oxide matrixes, especially Si02, Ti02, ZrO or
CaC03, or Si matrixes.
Medium containing photonic particles
The photonic particles may be contained in a
cosmetically acceptable medium, i.e. a non•toxic medium
suitable for application to human keratinous materials,
in particular the skin, mucous membranes, or the hair or
the nails.
Said medium is adapted to the nature of the support
onto which the composition is to be applied and to the
form in which the composition is to be packaged.
The medium may comprise a phase that is liquid at
25°C, containing photonic particles.
The medium may be selected so as to encourage
dispersion of the photonic particles in the medium before
application thereof, in order to prevent the photonic
particles from becoming aggregated. As an example, it
may be possible to use one or more agents that reduce the
surface tension of the medium containing the photonic
particles to less than 35 mN/m [millinewtons per meter].
The medium may be aqueous, with the photonic
particles contained in an aqueous phase. The term
"aqueous medium" denotes a medium that is liquid at
ambient temperature and atmospheric pressure and contains
a large fraction of water relative to the total weight of
the medium. The complementary fraction may contain or be
constituted by cosmetically acceptable organic solvents,
miscibie with water, for example alcohols or alkylene
glycols. The quantity of water in the aqueous medium is,
for example, 30% by weight or more, preferably 40% or
more preferably 50%.
The medium may be monophase or multiphase.
The medium may comprise an alcohol, such as ethanol
or isopropanol, for example, or a glycol derivative, in
particular ethylene glycol or propylene glycol.
The medium may be transparent or translucent, and
colored or not colored. The medium containing the
photonic particles may contain no pigment or colorant.
The coloration of the medium may be due ;o adding an
additional coloring agent.
The medium may comprise a volatile solvant. The
term "volatile solvant" as used in the context of the •
invention means any liquid capable of evaporating in
contact with keratinous materials, at arJoient temperature
and at atmcspheric pressure.
The medium may in particular be selected such that
the composition contains at least 5%, or even s.t least
30% of volatile solvant.
The medium nay comprise a film•forming polymer
improving protection persistence.
Film•forming polymer
In the present invention, the term "film•forming
polymer" means a polymer that, by itself or in the
presence of an auxiliary film•forming agent, is capable
of forming a macroscopically continuous film that adheres
to keratinous material, preferably a cohesive film, and
more preferably a film of cohesion and mechanical
properties that are such that said film can be isolated
and manipulated in isolation, for example when said film
is produced by casting over a non•stick surface such as a
Teflon or silicone surface.
The composition may comprise an aqueous phase and
the film•forming polymer may be present in said aqueous
phase. It is then preferably a polymer in dispersion or
an amphiphilic or associative polymer.
The term "polymer in dispersion" means polymers that
are insoluble in water, in the form of particles of
various sizes. The polymer may optionally be cured. The
mean particle size is typically in the range 25 nm to
50G nm, preferably in the range 50 nm to 200 nm. The
following polymers in aqueous dispersion may be used:
Ultrasol 2075® from Ganz Chemical, Daitosol 5000AD® from
Daito Kasei, Avalure OR 450® from Noveon, DYNAMX® from
National Starch, Syntran 5760® from Interpolymer, Acusol
OP 301® from RohmsHaas, and Neocryl A 1030® from Avecia.
Acrylic dispersions sold under the names Neocryl
XK•90®, Neocryl A•1073®, Neocryl A•109C®, Neocryl
BT•62®, Neocryl A•1079® and Neocryl A•523® by the
supplier AVECIA•NEORESINS, Dow Latex 422® by the supplier
DOW CHEMICAL, Darcosol 53C0 AD® or Daitosol 5000 SJ® by
the supplier DAITO KASEY KOGYO, Syntran 5760® by the
supplier Interpolymer, Aliianz OPI by the supplier ROHM 5
HAAS, aqueous dispersions of acrylic or styrene/acrylic
polymers sold under the trade name JONCRYL® by the
supplier JOHNSON POLYMER, or aqueous dispersions of
polyurethane sold under the names Neorez R•961® and
Necrez R•974® by the supplier AVKCIA•NE0RE5INS, Avalure
UR•405®, Avalure UR•410®, Avalure UR•425®, Avalure
UR•450®, Sancure 875®, Sancure 861®, Sancure 878® and
Sancure 2060® by the supplier GOODRICH, Impranil 85® by
the supplier BAYER, Aquamere H•1511® by the supplier
HYDROKER, sulfopolyesters sold under the trade name
Eastman AQ® by the supplier Eastman Chemical Products,
vinyl dispersions such as Mexomere PAM® from the supplier
CHIMEX and mixtures thereof, are other examples of
aqueous dispersions of particles of hydrcdisperslble
film•forming polymers.
The term "amphiphilic or associative polymers" means
polymers comprising one or more hydrophilic portions that
render them partially soluble in water and one or more
hydrophobic portions via which the polymers associate or
interact. The following associative polymers may be
used: Nuvis FX1100® from Elementis, Aculyn 22®, Aculyn
44®, Aculyn 46® from Rohm&Haas, and Viscophobe DB1000®
from Amerchol. Diblock copolymers constituted by a
hydrophilic block (polyacrylate, polyethylene glycol) and
a hydrophobic block (polystyrene, polysiloxane) may also
be used.
The composition may comprise an oily phase and the
film•forming polymer may be present in said oily phase.
The polymer may then be in dispersion or in solution.
NAD type polymers or microgels (for example KSGs) may be
used, as well as polymers of the PS•PA type or copolymers
based or. styrene (Kraton, Regalite) .
Examples of non•aqueous dispersions of polymer
particles in one or more silicone and/or hydrocarbon oils
that can be stabilized at their surface by at least one
stabilizing agent, in particular a block, graft or random
polymer and that may be mentioned are acrylic dispersions
in isododecane, such as Mexomere PAP® from the supplier
CHIMEX, ar.d dispersions of particles cf 3 graft ethylenic
polymer, preferably acrylic. In a liquid fatty phase, the
ethylenic polymer advantageously being dispersed in the
absence of additional stabilizer on the surface of
particles such as that described in particular in the
document WO 04/055081.
Film•forming polymers that may be used in the
composition of the present invention and that may be
mentioned are synthetic polymers.of the radical or.
polycondensation type, polymers of natural origin, and
mi xtures thereof.
In particular, the radical type film•forming
polymers may be polymers or copolymers, which are vinyls,
especially acrylic polymers.
Vinyl film•forming polymers may result from
polymerizing monomers containing an ethylenically
unsaturated bond having at least one acid group and/or
esters of said acid monomers and/or amides of said acid
monomers, such as unsaturated a, 13•ethylenically
unsaturated carboxylic acids, e.g. acrylic acid,
mefhacrylic acid, crotonic acid, maleic acid or itaconic
acid.
The polymers of natural origin, optionally modified,
may be selected from shellac resin, sandarac gum,
dammars, elemis, copals, and cellulose polymers such as
nitrocellulose, ethylcellulose or nitrocellulose esters
selected, for example, from cellulose acetate, cellulose
acetobutyrate, cellulose acetopropionate, and mixtures
thereof.
The film•forming polymer may be present in the form
of solid particles in aqueous or oily dispersion,
generally known as a latex or pseudolatex. The film•
forming polymer may comprise one or more stable
dispersions of particles of generally spherical polymers
of one or more polymers, in a physiologically acceptable
liquid fatty phase. These dispersions are generally
termeo polymer NADs, as opposed to latexes that are
aqueous polymer dispersions. These dispersions may be in
the form of nanoparticies of polymers in stable
dispersion in said fatty phase. The nanoparticie size is
preferably in the range 5 nm to 600 nra. The techniques
for preparing said dispersions are well known to the
skilled person.
The composition may comprise at least one film•
forming polymer that is a linear, block, ethylenic film•
forming polymer. Said polymer may comprise at least one
first sequence (block) and at least one second sequence
having different glass transition temperatures (Tg), said
first and second sequences being connected together via
an intermediate sequence comprising at least one
constitutive monomer of the first sequence and at least
one constitutive monomer of the second sequence. As an
example, the firsr. and second sequences and the block
polymer may be incompatible with each other. Such
polymers, for example, are described in the documents EF
1 411 069 or WO 04/028488, which are herewith
incorporated by reference.
Fatty Phase
Although the composition containing the photcnic
particles may be free of oil, in some implementations the
composition of the invention may include a fatty phase.
The photonic particles may optionally be contained in
said fatty phase.
The fatty phase may In particular be volatile.
The composition may comprise an oil such as, for
example, synthesized esters or ethers, linear or branched
hydrocarbons of mineral or synthetic origin, fatcy
alcohols containing 6 to 26 carbon atoms, partially
fluorinated hydrocarbon and/or silicone oils, silicone
oils such as polymethylsiloxanes (PDM3), which may
optionally be volatile, with a linear or cyclic silicone
chain, which may be liquid or pas~y at ambient
temperature, and mixtures thereof; other examples are
given below.
A composition in accordance with the invention may
thus comprise at least one volatile oil.
Volatile oils
In the context of the present invention, the term
"volatile oil" means an oil (or non•aqueous medium) that
is capable of evaporating on contact with skin in less
than one hour, at ambient temperature and.at atmospheric
pressure.
The volatile oil is a volatile cosmetic oil, liquid
at ambient temperature, in particular having a non•zero
vapor pressure, at ambient temperature and atmospheric
pressure, in particular having a vapor pressure in the
range 0.13 Pa to 40000 Pa (10~5 mmHg to 300 mmHg) , in
particular in the range 1.3 Pa to 13000 Pa (0.01 mmHg to
100 mmHg), and more particularly in the range 1.3 Pa to
1300 Pa (0.01 mmHg to 10 mmHg).
The volatile hydrocarbon oils may be selected from
hydrocarbon oils of animal or vegetable origin containing
8 to 16 carbon atoms, and in particular branched C3•C16
alkanes (also termed isoparaffins), such as isododecane
(also termed 2, 2, 4, 4, 6•per.tamethyiheptane) , isodecane,
isohexadecane, and, for example, oils sold under the
trade names Isopars'"1 or Permethyls®.
Examples of volatile oils that may also be used are
volatile silicones, for example linear or cyclic volatile
silicone oils, especially those with a viscosity
of <8 cenristokes (3 X 10~° m2/s) , especially containing 2
to 10 silicon atoms, in particular 2 to 7 silicon atoms,
said silicones optionally comprising alkyl or alkoxy
groups containing 1 to 10 carbon atoms. Examples of
volatile silicone oils ohat may be used•in the invention
that may be mentioned are dimethicones with a viscosity
of 5 est to 6 est, octamethyl cyclotetrasiloxane,
decamethyl cyciopentasiloxane, dodecamethyl
cyciohexasiloxane, heptamethyl hexyltrisiloxane,
hepramethyloctyl trisiloxane, hexamethyl disiloxane,
octamethyl trisiloxane, decamethyl tetrasiloxane,
dodecamethyl pentasiloxane, and mixtures thereof.
It is also possible to use fluorinated volatile oils
such as nonafluorcmethoxybutane or
perfluoromethylcyclopentaiief and mixtures thereof.
It is also possible to use a mixture of the oils
mentioned above.
Ncn•vciatile oils
A composition of the invention may comprise a non-
volatile oil.
Within the context of the present invention,, the
term "r.on•volatile oil" means an oil having a vapor
pressure cf less than 0.13 Pa, in particular high
molecular mass oils.
The non•volatile oils may in particular be selected
from hydrocarbon oils, fluorinated where appropriate,
and/or non•volatile silicone oils.
Examples of non•volatile hydrocarbon oils that may
be suitable for implementing the invention that may in
particular be mentioned are:
• hydrocarbon oils of animal origin;
• hydrocarbon oils of vegetable origin, such as
phytostearyl esters, for example phytostearyl oleate,
physostearyl isostearate or lauroyl / octyldodecyl /
phytostearyl glutamate sold, for example, under the name
ELDEW PS203 by AJINOMOTO, triglycerides constituted by
esters of fatty acids and glycerol in which the fatty
acids may have chain lengths in the range C4 to C24/ and
may be linear or branched, saturated or unsaturated; said
oils are in particular heptanoic or octanoic
triglycerides, or wheatgerm, sunflower, grapeseed,
sesame, corn, apricot, castor, shea, avocado, olive,
soya, sweet almond, palm, rape, cottonseed, ha2elnnt,
macadamsa nut, jojoba, alfalfa, peppy, Hokaido squash,
gourd, blackcurrant, evening primrose, millet, barley,
quinoa, rye, carthame, bancoulier, passiflora, or musk
rose oils; shea butter; or caprylic / capric acid
triglycerides such as those sold by the supplier
STEARTNERIES DUBOIS OR those sold under the names MIGLYCL
810®, 812® and 318® by the supplier DYMAMIT NOBEL;
• hydrocarbon oils of mineral or synthetic origin•
such as, for example:
o synthesized ethers containing 10 to 4 0 carbon
atoms;
o linear or branched hydrocarbons of mineral or
synthetic origin, such as vaseline, pclydecenes,
hydrogenated poiyisobutene such as parleam, squalane and
mixtures thereof, and in particular hydrogenated
poiyisobutene; and
o synthesized esters such as oils with formula
RiCOOR2/ wherein Ri represents the residue of a linear or
branched fatty acid containing 1 to 40 carbon atoms and R2
represents a hydrocarbon chain, especially branched,
containing 1 to 40 carbon atoms,, provided that Ri + R2 S
10.
The esters may be in particular be selected from
esters, in particular of fatty acids such as, for
example:
• cetostearyl octanoate, esters of isopropyl alcohol
such as isopropyl myristate, isopropyl paimitate, ethyl
paimitate, 2•erhyi•hexyl paimitate, isopropyl stearate or
isostearate, isostearyl isostearate, octyl stearate,
hydroxy1 esters such as isostearyl lactate, octyl
hydroxystearate, diisopropyl adipate, heptanoates, in
particular isostearyl heptanoate, octanoares, decanoates
or ricinoleates of alcohols or polyalcohols, such as
propylene glycol dioctanoate, cetyl octanoate, tridecyl
octanoate, 2•ethylhexyl 4•diheptanoate and paimitate,
alkyi benzoate, polyethylene glycol diheptanoate,
propylenegiycol 2•diethyl hexanoate and mixtures thereof,
C12•C15 alcohol benzoates, hexyl laurate, neopentanoic acid
esters such as isodecyl r.ecpentancate, isotridecyl
neopentansate, iscstearyl neopertar.oate, cctyldodecyl
necpentanoate, iscnonar.oic acid esters such as iscnonyl
iscnonanoatef isotridecyl isononanoa~e, octyl
iscnonanoate, or hydroxy1 esters such as isostearyl
lactate, or di•isostearyl malate;
• esters of polyols, and pentaetrythritoi esters,
such as dipentaerythritol tetrahydroxystearat /
tetraisostearate;
• esters of diol dimers.and diacid dimers, such as
Lusplan DD•DA5© and Lusplan DD•DA7®, sold by the supplier
NIPPON FINE CHEMICAL and described in application FR 03
0280 9;
• fatty alcohols that are liquid at ambient
temperature having a branched and/or unsaturated carbon
chain containing 12 to 26 carbon atoms, such as 2•
octyldodecanol, isostearyl alcohol, oleic alcohol, 2•
hexyldecanol, 2~butylcctanol, or 2•undecylpentadecanol;
• higher fatty acids such as oleic acid, lincleic
acid, linolenic acid and mixtures thereof; and
• dialkyl carbonates, one 2 alkyl chains possibly
being identical or different, such as dicaprylyl
carbonate sold under the name Cetiol CC©, by Cognis;
• non•volatile silicone oils such as, for example,
non•volatile polydimethylsiloxanes (PDMS),
polydimethylsiloxanes comprising pendant alkyl or alkoxy
groups and/or with silicone chain ends, groups each
containing 2 to 24 carbon atoms, phenyl silicones such as
phenyl trimethicones, phenyl dimethicones, phenyl
trimethylsiloxy diphenyisiloxanes, diphenyl dimethicones,
diphenyl methyldiphenyl trisiloxanes, or 2•phenylethyl
trimethylsfloxysilicates, or dimethicones or
phenyltrimethicone with a viscosity less than or equal to
103 cSt, and mixtures thereof;
• and mixtures thereof.
The composition containing photonic particles may be
free of oil, and in particular nay contain no non-
volatile oil.
Complementary screens and additives
The composition comprising photonic particles may
comprise at least, one additive selected from adjuvants
that are normal in the cosmetics field, such as fillers,
coloring agents, hydrophilic or lipophilic gelling
agents, active ingredients, either hydrosoluble or
liposoluble, preservatives, moisturizers such as polyols
and in.particular glycerin, sequestrating, agents,
antioxidants, solvents, fragrances, physical and chemical
sunscreens, especially against UVA and/or UVB, odor
absorbers, pH adjusting agents (acids or bases), and
mixtures thereof.
The composition may contain at least one active
ingredient having a complementary activity in the sclar
protection field, such as antioxidants, whitening agents
in the context of anti•pigmentaticn and depigmentation,
or anti•ageing active ingredients.
The additional organic screens, either hydrophobic,
hydrophilic or insoluble in the usual solvents, may be
selected from various categories of chemical compounds.
In particular, the organic screens are selected from
dibenzoylmethane derivatives; anthranilates; cinnamic
derivatives; salicylic derivatives, camphor derivatives;
benzophenone derivatives; B,p•diphenylacrylate
derivatives; triazine derivatives other than those with
formula (I); benzalmalonate derivatives, in particular
those mentioned in patent US 5 624 663; benzimidazole
derivatives; imidazolines; p•amincbenzoic acid (PABA)
derivatives; benzotriazole derivatives; methylene bis•
(hydroxyphenyl benzctriazole) derivatives such as those
described in applications US 5 237 071, US 5 166 355,
GB 2 303 549, DE 137 26 184 and E? 0 393 119; benzoxazole
derivatives such as those described in patent
applications E? 0 332 642, EP 1 027 383, EP 1 300 137 and
DE 01 62 S44; polymer screens and silicone screens such
as those described in particular in application
WO 93/04665; dimers derived from a•alkylstyrer_e, such as
those described in patent application DE 198 55 649; 4,4•
diarylbutadier.es such as those described in applications
EP 0 967 200, DE 197 46 654, DE 197 55 649,
EP A 1 008 586, EP, 1 133 980 and EP 0 133 981; or
merocyanin derivatives such as those described in
applications WO 04/006878, WO 05/C58269 and WO 06/032741,
and mixtures thereof.
The screen or screens may be selected from the
following screens:
Hydrophobic screens capable of absorbing UV in the range
320 nm to 400 nm (UVA)
Dibenzoylmethane derivatives
Butyl ir.ethoxydibenzoylmethane sold in particular
under the trade name "PARSOL 1789" by DSM Nutritional
Products, Inc;
• Isopropyl dibenzoylmethane.
Aminobenzcphenones
n•hexyl 2•(4•diethylamino•2•hydroxybenzoyl)•benzoate sold
under the trade name "UVINUL A+" by BASF.
Anthranilic derivatives
Menthyl anthranilate sold under the trade name "NEO
HELIOPAN MA" by SYMRISE.
4f4•diarylbutadiene. derivatives
1,1•dicarboxy (2,2'•dimethyl•propyl}•4,4•
diphenylbutadiene.
Preferred screens are butyl methoxydibenzoylmethane
and n•hexyl 2•(4•diethylamino•2•hydroxybenzoyl)•benzoate.
Hydrophobic screens capable of absorbing UV in the range
280 nm to 320 nm (CVB)
Para•air.inobenzcates
Ethyl PABA;
Ethyl dihydroxypropyl PABA;
Sthylhexyl dimethyl PABA (ESCALOL 507 from ISP).
Salicylic derivatives
Homosalate sold under the name "Eusolex HMS" by
Rona/EM Industries;
• Ethylhexyi salicylate sold under the name "NEO
HELIOPAN OS" by SYMRISE;
• Dipropyleneglycol salicylate sold under the name
"DIPSAL" by SCHER;
• TEA salicylate, sold under the name "NEO HELIOPAN
TS" by SYMRISE.
Cirjrjam3te.s
Ethylhexyi methoxycinnamate sold in particular under
the trade name "PARSOI MCX" by DSM Nutritional Products,
Inc;
• Isopropyl methoxy cirmamate;
• Isoamyl methoxy cinnamate sold under the trade
name "NEO HELIOPAN E 1000" by SYMRISE;
• Diisopropyl metnylcinnamate;
• Cinoxate;
• Glyceryl ethylhexanoate dimethoxycinnamate.
P,p' •diphenylacrylate derivatives•
Octocryiene, sold in particular under the trade name
"UVINUL N539" by BASF;
• Etccrylene, sold in particular under the trade
name "UVINUL N35" by BASF.
Benzylidene camphor derivatives
3•Benzylidene camphor manufactured under the trade
name "MEXORIL SD" by CH1MEX;
• Methylbenzylidene camphor sold under the trade
name "EUSOLEX 6300" by MERCK;
• Polyacrylamidomethyl benzylidene camphor
manufactured under the name "MEXORYL SW" by CHINEX.
Triazine tioriyatives
Ethylhexyl triazone cold in particular under the
trade name "UVINUL T150" by BASE;
• Diethylhexyl butamido triazone sold under the
trade name "UVASORB HKB" by SIGMA 3V;
• 2,4,.6•tris(dineopentyl 4'•amino benzalmalonate)•s•
triazine;
• 2,4, 6•tris•(diisobutyl 4'•amino benzalmalonate)•s•
triazine;
• 2, 4•bis (dineopentyl 4 ' •amino benzalmalonate) •6•
(4'• n•butyl aminobenzoate)•s•triazine;
• 2, 4•bis (n•butyl 4 ' •amino ber.zoate) •6•
(aminopropy]trisiioxane)•s•triazine;
• symmetrical triazine screens described in patent
US 6 225 467, application WO 2004/085412 (see compounds 6
to 9) or the document "Symmetrical Triazine Derivatives",
IP.COM Journal, TP.COM INC WEST HENRIETTA, NY, US (20
September 2004), in particular 2,4,6•tris•
(biphenyl)•1,3,5•triazine (in particular 2,4,6•
tris (biphenyl•4•yI•l,3,5•triazine) and 2, 4, 6•
tris(terphenyl)•1,3,5•triazine that is discussed in
applications by BEIERSDORF, numbers WO 06/035000,
WO 06/034982, WO 06/034991, WO 06/035007, WO 2006/034992,
WO 2006/034985.
Imidazoline derivatives
Ethylhexyl dimethoxybenzylidene dioxoimidaz•oline
propionate.
Ben z alma. Ion ate derivati ve s .
Pclyorganosiloxanes having a benzalmalonate
function, such as Polysilicone•15 sold under the trade
name "PARSOL SLX" by DSM Nutritional Products, Inc;
• di•neopentyl 4 f•mechoxybenzalmaionate.
Merocyanin derivatives
Octyl•5•N,N•diethylamino•2•phenysulfonyl•2,4•
pentadienoate.
Preferred screens are homosalate,
ethyihexylsalicylate, octocrylene, ethylhexyl,
methoxycinnamate v, isoamyl methoxycinnamate, ethylhexyl
trj.azone, and diethylhexyl butamido triazone.
The most preferred compounds are
ethyihexylsalicylate, octocrylene, ethylhexyl triazone
and ethylhexy.1 methoxycinnamate.
Mixed hydrophobic screens capable of absorbing both UVA
and UVB
Benzophenone derivatives
Benzcphenone•1 sold under the trade name "UVINUL
4 00" by BASF;
• benzophenone•2 sold under the trade name "UVINUL
D5 0" by BASF;
• Benzophenone•3 or oxybenzone, sold under the trade
name "UVINUL M40" by BASF;
• benzophenone•5;
• benzophenone•6 sold under the trade name "Kelisorb
11" by Norquay
benzophenone•8 sold under the trade name "Spectra•Sorb
UV•24" by American Cyanamid;
• benzophenone•10;
• benzophenone•11;
• benzophenone•12.
Phenyl benzotriazole derivatives
Drometrizole trisiloxane sold under the name
"Silatrizole" by RHODIA CHIMIE;
• methylene bis•benzotriazoiyl
tezramethylbutylphenol, sold in the solid form under the
trade name "MIXXIM B3/100" by FAIRMOUNT CHEMICAL or in
micron:.zed form in aqueous dispersion under the trade
name "TINOSORR M" by CI3A SPECIALTY CHEMICALS.
Bis•resorcinyl_ triazlne derivatives
Bis•ethylhexyloxyphenol methoxyphenyl triazine sold
under the trade name "TINOSGRB S" by .CIBA GEIGY.
Benzoxazole derivatives
2 , 4•bis• [5•1 (diinethylpropyl) benzoxazol•2•yl• (4•
phenyl)•iminoj•6•(2•ethylhexyl)•imino•1,3,5•triazine sold
under the name Uvasorb K2A by Sigma 3V.
The preferred screens are:
• drometrizole trisiloxane;
• methylene bis•benzotriazolyl
tetramethylbutylphenol;
• bis•ethylhexyloxyphenol methoxyphenyl triazine;
and
• benzophenone•3 or cxybenzone.
The most preferred are:
• drometrizole trisiloxane; and
• bis•ethylhexyloxyphenol methoxyphenyl triazine
Bydrosoluble screens capable of absorbing UV in the range
320 nm to 400 nm (UVA)
Terephthalylidene dicamphor acid sulfonic acid
manufactured under the name "MEXCRYL SX" by CHIMEX.
Bis•benzoazolyi derivatives as described in patents
EP 0 669 323 and US 2 463 264, more particularly the
compound discdium phenyl dibenzimidazole tetrasulfonate
sold under the trade name "NEO HELIOPAN AP" by Haarmann
and REIMER.
The preferred screen is terephthalylidene dicamphor
acid sulfonic acid.
Hydrosoluble screens capable of absorbing UV in the range
280 nm to 320 nm (UVB)
p•aminohenzoic derivatives (PABA)
PABA;
• glyceryl PABA; and
• PEG•25 PABA sold under the name "UVINUL P25" by
BASF;
• phenylbenzimidazole sulfonic acid sold in .
particular under the trade name "EUSOLEX 2 32" by MERCK;
• ferulic acid;
• salicylic acid;
• DEA methoxycinnamate;
• benzylidene camphor sulfonic acid manufactured
under the name "MEXORYL SL" by CHIMEX;
• camphor benzalkonium methosulfate manufactured
under the name "MEXORYL SO" by CHIMEX; and
• The preferred screen is phenylbenzimidazole
sulfonic acid.
Mixed UVA and UVB hydrosoluble screens
Benzophenone derivatives comprising at least one sulfonic
radical
Benzophenone•4 sold under the trade name "UVINUL
MS40" by BASF;
• benzophenone•5; and
• benzophenone•9.
The preferred screen is benzophenone•4.
The organic screen or screens of the invention may
be present in the compositions of the invention in a
concentration in the range 0.1% to 15%, preferably in the
range 0.2% to 10%, by weight relative to the total
composition weight.
Inorganic sunscreens or photoprotectors
The inorganic photcprotactive agents are selected
from metallic oxide pigments that may optionally be
coated (mean size of primary particles: generally in the
range 5 nm to 100 nm, preferably in the range 10 nm tc
50 nm), such as titanium oxide pigments (amorphous or
crystalline in the form of rutile and/or anatasc), iron,
zinc, zirconium, or cerium, which are all UV
photoprotectors that are well known per eg.
The pigments may optionally be coated.
The coated pigments are. pigments that have undergone
one or more surface treatments of a chemical, electronic,
or chemical•mechanical nature with compounds such as
those described in Cosmetics & Toiletries, February
1390, Vol 105, pp. 53 • 64, such as amino acids, beeswax,
fatty acids, fatty alcohols, anionic surfactants,
lecithins, sodium, potassium, zinc, iron, or aluminum
salts of fatty acids, metallic (titanium or aluminum)
alkoxides, polyethylene, silicones, proteins (collagen,
elastin), alkanolamines, oxides of silicon, metallic
oxides or sodium hexametaphosphate.
In known manner, the silicones are organo•silicon
polymers or oligomers with a linear or cyclic, branched
or cured structure, with a variable molecular weight
obtained by polymerization and/or polycondensation of
suitably funcnicnalized silanes and essentially
constituted by repeated principal motifs in which the
silicon atoms are connected together via oxygen atoms
(siloxane linkage), with hydrocarbon radicals that may be
substituted being directly bonded via a carbon atom to
said silicon atoms.
The term "silicones" also encompasses pigments that
are necessary for their preparation, in particular
alkylsilanes.
The silicones that are used for coating pigments for
suitable use in the present invention are preferably
selected from the group containing alkyl silanes,
poiydialkyisilcxanes and poiyalkylhydrogenosiloxanes.
S~ill more preferably, ~he silicones are selected from
the group containing cc~yl trimethyl silane,
polydimethylsiloxanes and polymethylhydrogenosiioxanes.
Clearly, prior to treating them with silicones, the
metallic oxide pigments may have been treated with other
surface agents, in particular with cerium oxide, alumina,
silica, aluminum compounds, silicon compounds, or
mixtures thereof.
More particularly, • the coated pigments are titanium
oxides coated with the following:
• silica, such as the product "SUNVEIL" from the
supplier IKEDA;
• silica and iron oxide, such as the product
"SUNVEIL V" from the supplier IKEDA;
• silica and alumina, such as the products
"MICRO!ITANIUM DIOXIDE MT 500 SA" and "MICROTITANIUM
DIOXIDE MT 100 SA" from the supplier TAYCA, or "TICVEIL"
from the supplier TIOXIDE;
• alumina, such as the products "TIPAQUE TTO•55 (B)"
or "TIPAQCE TTO•55 (A)" from the supplier ISHIHARA, and
"UVT 14/4" from the supplier KEMIRA;
• alumina and aluminum stearate, such as the
products "MICROTITANIUM DIOXIDE MT 100 T, MT 100 TX, MT
100 Z, MT•01" from the supplier TAYCA, the product
"Solaveil CT•10 W" and "Solaveil CT 100" from the
supplier UNIQEMA, and the product "Eusolex T•AVO" from the
supplier MERCK;
• silica, alumina and alginic acid, such as the
product "MT•100 AQ" from the supplier TAYCA;
• alumina and aluminum laurate, such as the product
"MICROTITANIUM DIOXIDE MT 100 S" from the supplier TAYCA;
• iron oxide and iron stearate, such as the producr.
"MICRCTITANIUM DIOXIDE MT 100 F" from the supplier TAYCA;
• zinc oxide and zinc stearate, such as the product
"BR 351" from the supplier TAYCA;
• silica and alumina trea.ed with a silicone, such
as the product "MICROTITANIUM DIOXIDE MT 600 SAS",
"MICROTITANIUM DIOXIDE MT 500 SAS", or "MICROTITANIUM
DIOXIDE MT 100 SAS" from the supplier TAYCA;
• silica, alumina, and aluminum st.earate treated
with a silicone, such as the products "STT•30•DS" from
the supplier TITAN KOGYO;
• silica treated with a silicone, such as the
product "UV•TITAN X 195" from the supplier KEMIRA;
• alumina treated with a silicone, such as the
products "TIPAQUE TTO•55 (S)" from the supplier ISHIHARA,
or "DV TITAN M 262" from the supplier KEMIRA;
• triethanolamine, such as the product "STT•65•S"
from the supplier TITAN KOGYO;
• stearic acid, such as the product "TIPAQOE TTO•55
(C)" from the supplier ISKIHARA;
• sodium hexametaphosphate, such as the product
"MICROTITANIUM DIOXIDE MT 150 W" from the supplier TAYCA;
' TiOs treated with octyl trimethyl silane, sold
under the trade name "T 8C5" by the supplier DEGUSSA
SILICES;
• Ti02 treated with a polydimethylsiloxane, sold
under the trade name "7025C Cardre UF T102SI3" by the
supplier CARDRE;
• Ti02 anatase/rutile treated with a
polydimethylhydrogenosiloxane sold under the trade name
"MICRO TITANIUM DIOXIDE USP GRADE HYDROPHOBIC" by the
supplier COLOR TECHNIQUES.
Uncoated titanium oxide pigments are, for example,
sold by the supplier TAYCA under the trade names
"MICROTITANIUM DIOXIDE MT 500 B" or "MICROTITANIUM
DIOXIDE MT60C B", by the supplier DEGUSSA under the name
"P 2 5",• by the supplier WACKER under the name
"Transparent fitar.iuit oxide PW", by the supplier MIYOSHI
KASEI under the name "UFTR", by the supplier TOMEN under
the name "ITS" and by the supplier TIOXIDE under the name
"TIOVEIL AQ".
Examples of uncoated zinc oxide pigments are:
• those sold under the name "Z•cote" by the supplier
Sunsmart;
• those sold under the name "Nanox" by the supplier
Elementis;
• those sold under the name "Nanogard WCD 2025" by
the supplier Nanophase Technologies.
Examples of coated zinc oxide pigments are:
• those sold under the name "Zinc oxide CS-5" by the
supplier Toshibi (ZnO coated with
polymethylhydrogenosiloxane);
• those sold under the name "Nanogard Zinc Oxide FN"
by the supplier Nanophase Technologies (40% dispersion in
Finsolv IN, C12-C15 alcohol benzoate);
• those sold under the name "DAITOPERSION ZN-30" and
"DAITCPERSION Zn-50" by the supplier Daito (dispersions
in cyclopolymethylsiloxane / oxyethylenated
polydimethylsiloxane, containing 30% to 50% of nano-zinc
oxides coated with silica and
polymethylhydrogenosiloxane);
• those sold under the name "NFD Ultrafine ZnO" by
the supplier Daikin (ZnO coated with perfluoroalkyl
phosphate and copolymer based on perfluoroalkylethyl in
dispersion in cyclopentasiloxane);
• those sold under the name "SPD-Z1" by the supplier
Shin•Etsu (ZnO coated with silicone-grafred acrylic
polymer, dispersed in cyclodimethylsiloxane);
• those sold under the name "Escalol Z100" by the
supplier ISP (ZnO-treated alumina dispersed in an
ethylhexyl methoxycinnamate / PVP•hexadecene copolymer /
methicone mixture);
• these sold under the name "Fuji ZnO-SMS-10" by the
supplier Fuji Pigment (ZnO coated with silica and
polymethylsilsesquicxane);
• those sold under the name "Nanox Gel TN" by the
supplier Elementis (ZnO dispersed in a concentration of
55% in C12-C15 alcohol benzoate with polycondensate of
hydroxystearic acid).
Uncoated cerium oxide pigments are sold under the
name "COLLOIDAL CERIUM OXIDE" by the supplier RHONE
POULENC.
Uncoated iron oxide pigments are sold, for example,
by the supplier ARNAUD under the names "NANOGARD WCD 2002
(FE 45B)",."NANOGARD IRON FE 45 BL AQ", "NANOGARD FE 45R
AQ", "NANOGARD WCD 2006 (FE 45R)", or by the supplier
MITSUBISHI under the name "TY-220".
Coated iron oxide pigments are, for example, sold by
the supplier ARNAUD under the names "NANOGARD WCD 2008
(FE 45B FN)", "NANOGARD WCD 2009 (FE 453 556)", "NANOGARD
FE 45 BL 345", "NANOGARD FE 45 BL", or by the supplier
BASF under the name "TRANSPARENT IRON OXIDE".
Mention may also be made of mixtures of metallic
oxides, in particular of titanium dioxide and of cerium
dioxide, including the mixture of equal weights of
titanium dioxide and cerium dioxide coated with silica,
sold by the supplier IKEDA under the name "SUNVEIL A", as
well as a mixture of titanium dioxide and zinc dioxide
coated with alumina, silica and silicone, such as the
product "K 261" sold by the supplier KEMIRA, or coated
with alumina, silica and glycerin, such as the product
"M 211" sold by the supplier KEMIRA.
The inorganic screen or screens may be present in
the compositions of the invention in a concentration in
the range 0.1% to 15%, preferably in the range 0.2% to
10%, by weight relative to the total composition weight.
The additive or additives may be selected from those
mentioned in 'he CTFA Cosmetic Ingredient Handbook, 10th
Edition, Cosmetic and Fragrance Assn, Inc., Washington DC
(2004), herewith incorporated by reference.
Galenical forms
The photonic particles may be used in lotions,
creams, milks, pcmmades, gels, films, patches, sticks,
powder, pastes, for the skin, the lips, the hair or the
nails.
Modes of application
The composition comprising photonic particles may be
applied by hand or using an applicator.
Application may also be carried out by spraying or
projection using a piezoelectric device, for example, or
by transferring a layer of composition that has been
deposited on an intermediate support.
Packaging
The composition may be packaged in any packaging
device, especially formed from thermoplastic material, or
on any support provided for that purpose.
The packaging device may be a bottle, a pump bottle,
an aerosol bottle, a tube, a sachet or a pot.
Example
Nanoparticles are constituted by 100% of 285 nm PMMA
nanoparticles from the supplier SOKEN.
The photonic particles, obtained by spray drying,
were approximately 30 µm in size.
Figure 4 represents an absorption spectrum cf
various compositions comprising photonic particles of the
invention.
Unless otherwise specified, the expression
"comprising a" should be construed as meaning "comprising
at least one".
CLAIMS
1. A method of photoprotecting a material against solar
UV radiation, comprising treating said material using
a composition or integrating said composition into
said material,
wherein said composition comprises a dispersion of
photonic particles with a mean size in the range 1 µm
to 500 pro, each photonic particle comprising a
diffracting arrangement of monodisperse nanoparticles
or voids, the diffraction spectrum of said arrangement
including a first order reflection peak in the
wavelength range 250 nm to 400 nm.
2. A non-therapeutic, and in particular cosmetic, method
of photoprotecting human keratinous material against
solar UV radiation, comprising applying a cosmetic
composition comprising a dispersion of photonic
particles with a mean size in the range i µm to
500 µm, each comprising a diffracting arrangement of
monodisperse nanoparticles or voids, the diffraction
spectrum of said arrangement including a first order
reflection peak in the wavelength range 250 nm to
4 00 nm.
3. A method according to either one cf claims 1 and 2,
wherein the photonic particles comprise nanoparticles
aggregated without a matrix.
4. A method according to either one of claims 1 and 2,
wherein the photonic particles comprise nanoparticles
(13), aggregated or dispersed in a matrix (20).
5. A method according to any preceding claim, wherein the
mean site of the nanoparticles (10) is in the range
100 nm to 500 nm, preferably in the range 10 0 nm to
350 nm.
6. A method according to any preceding claim, wherein the
photonic particles (1) have a form factor of less than
2.
7. A method according to the preceding claim, wherein the
photonic particles (1) are substantially spherical in
shape.
8. A method according to any preceding claim, wherein the
composition includes an additional sunscreen and/or an
additional coloring agent.
9. A method according to any preceding claim, wherein the
content of the photonic particles (1) in the
composition is in the range 0.1% to 20% by weight.
before application.
10.A method according to any preceding claim, wherein at
least one photonic particle (1) includes at least one
other diffracting arrangement of nanoparticles (10),
especially two other arrangements, the arrangements
having different diffraction spectra.
11.A method according to the preceding claim, wherein the
different arrangements diffract light through
different zones of the photonic particle (1).
12. A method according to either one of the two preceding
claims, wherein one of the arrangements has a
diffraction spectrum having at leasrt one first order
reflection peak in the wavelength range 250 nm to
400 nm and another arrangement having a diffraction
spectrum exhibiting at least one firsr, order
reflection peak in the wavelength range 250 nm to
400 nm or 400 nm to 70 0 nm.
13.A method according to any one of claims 4 to 12,
wherein the matrix (20) is:
• an organic matrix selected from:
• acrylic polymethyl methaorylate (PMMA) or
polyacrylamide (PAM) matrixes, polyethylene
terephthalate (PET), polystyrene (PS),
polycaprolactone, polyvinyl acetate, or pclyvinylethyi
acetate matrixes, and waxes with a melting point of
more than 65°C and with a hardness of more than 5 MPa;
and
• organic crosslinkabie matrixes selected from:
photocrosslinkable polymers such as
ETPA (ethoxylated trimethylolpropanetriacrylate),
PEGDA (polyethyleneglycol diacrylate) , acrylic resins,
PEG diacrylates,
copolymers of polyvinyl acetate or
polyvinyiethyl acetate and of styrylpyridiniums with
the following formulae:

where R represents a hydrogen atom, or an alkyl or
hydroxyalkyl group, and R' represents a hydrogen atom
or an alkyl group;
-cinnamic acid derivatives such as
polyvinylcinnamate or PDMS cinnamate;
reactive silicones, i.e.:
- polyorganosiloxanes comprising
siloxane units with formula:

where R is a monovalent, linear or cyclic hydrocarbon
grcup containing 1 to 30 carbon atoms, m is equal to 1
or 2, and R' is an unsaturated aliphatic hydrocarbon
grcup containing 2 to 10 carbon atoms or an
unsaturated cyclic hydrocarbon group containing 5 to 8
carbon atoms;
- polyorganosiloxanes comprising at
least one alkylhydrogenosiloxane unit with formula:

where R is a monovalent, linear or cyclic, hydrocarbon
group containing 1 to 30 carbon atoms or a phenyl
group and P is equal to 1 to 2; and
thermoplastic, thermocrosslinkable or
electro-crosslinkable polymers;
an inorganic matrix selected from metallic oxides,
in particular SiO2, TiO2, ZrO, or an inorganic CaCO3 or
Si matrix.
14.A method according to any one of claims 1 to 13,
wherein the photonic particles (1) are colorless.
15.A method according to any preceding claim, wherein the
nanoparticles (10) have a mean size having a
coefficient of variation lying in the range 5 % to 15
16.A method according to any preceding claim, wherein the
photonic particles each have a mean size lying in the
range 1 to 50 urn, better 1 to 40 urn, better 1 to 2 0
ym.
17.A method according to any preceding claim, wherein the
composition comprises a single type of photonic
particle.
18.A method according to any preceding claim, wherein the
nanoparticles are inorganic and, in particular,
comprise silica.
19.A method according to any preceding claim, wherein the
photonic particles are of the direct cpal type.
20. A method according to any one of claims 4 to 18,
wherein the photonic particles are of the inverse opal
type.
21. A method according to any one of claims 4 to 20,
wherein the matrix does not comprise additional
nancparticles, in particular of metal or metal oxide
type, different from the nanoparticles constituting
the diffracting arrangement.
22. A method of photoprotecting an ink, a paint or a
coating, comprising incorporating at least. one
composition comprising a dispersion of photonic
particles as defined in claims 1 tc 21 into said ink
or paint or coating.
23. A method of photoprotecting a material manufactured
from at least one synthetic or natural polymer,
comprising treating said polymer with at least one
composition comprising a dispersion of photonic
particles as defined in claims 1 to 21 or integrating
said composition into said material.
2 4.A method of photoprotecting an organic or
mineral glass, comprising treating said glass with at
least one composition comprising a dispersion of
photonic particles as defined in claims 1 to 21 or
comprising integrating said composition into said
glass.
25. A method of photoprotecting a material comprising at
least natural fibers and/or synthetic fibers such as
textiles or papers, comprising treating said material
with at least one composition comprising a dispersion
of photonic particles as defined in claims 1 to 21 or
comprising integrating said composition into said
material.
26.A composition for carrying out a method according to
any one of claims 22 to 25, comprising a dispersion of
photonjo particles (1) with a mean size in the range
1 urn to 500 urn, each comprising a diffracting
arrangement of monodisperse nanoparticles (10) or
voids, the diffraction spectrum of said arrangement
comprising a first order reflection peak in the
wavelength range 250 nm to 400 nm.
27.A photoprotective cosmetic composition for carrying
out a method according to any one of claims 1 to 26,
comprising a dispersion of photonic particles (1) with
a mean size in the range 1 µm to 500 urn, each
comprising a diffracting arrangement of monodisperse
nanoparticles (10) or voids, the diffraction spectrum
of said arrangement comprising a first order
reflection peak in the wavelength range 250 nm to
400 nm.
28.A composition according to claim 27, having a SPF of
more than 10.
23.A method of photoprotecting a material against solar
UV radiation, comprising treating said material using
a composition or integrating said composition into
said material,
wherein said composition comprises a dispersion of
photonic particles with a mean size in the range 1 µm
to 500 µm, each photonic particle comprising a
diffracting arrangement of monodisperse nanoparticles
or voids, the diffraction spectrum of said arrangement
including a first order reflection peak in the
wavelength range 250 nm to 400 nm,
wherein said photonic particles are of the direct opal
type and are substantially spherical in shape.
30. A method of photoprotecting a material against solar
UV radiation, comprising treating said material using
a composition or integrating said composition into
said material,
wherein said composition comprises a dispersion of
photonic particles with a mean size in the range 1 µm
to 500 µm, each photonic particle comprising a
diffracting arrangement of monodisperse nanoparticles
or voids, the diffraction spectrum of sard arrangement
including a first order reflection peak in the
wavelength range 250 nm to 400 nm,
wherein said photonic particles are of the inverse
opal type.
31.A non-therapeutic, and in particular cosmetic, method
of photoprotecting human keratinous material against
solar UV radiation, comprising applying a cosmetic
composition comprising a dispersion of photonic
particles with a mean size in the range 1 µm to
500 µm, each comprising a diffracting arrangement of
monodisperse nanoparticles or voids, the diffraction
spectrum of said arrangement including a first order
reflection peak in the wavelength range 250 nm to
4 00 nm,
wherein said photonic particles are of the direct opal
type and are substantially spherical in shape.
32.A non-therapeutic, and in particular cosmetic, method
of photoprotecting human keratinous material against
solar UV radiation, comprising applying a cosmetic
composition comprising a dispersion of photonic
particles with a mean size in the range 1 urn to
500 µm, each comprising a diffracting arrangement of
monodisperse nanoparticles cr voids, the diffraction
spectrum of said arrangement including a first order
reflection peak in the wavelength range 250 nm to
4 00 nm,
wherein said photonic particles are of the inverse
opal type.

ABSTRACT

The present invention provides a method of photoprotecting a material against solar UV radiation, consisting in
treating said material using a composition comprising a dispersion of photonic particles with a mean size in the range 1 µm to 500
µm, each comprising a diffracting arrangement of monodisperse nanoparticles or voids, the diffraction spectrum of said arrangement
including a first order reflection peak in the wavelength range 250 nm to 400 nm, or consisting in integrating said dispersion
of photonic particles into said material. In particular, the present invention provides methods of photoprotecting materials such as
paints, inks, coatings, materials manufactured from polymers, or fibrous materials such as textiles, papers, or organic or mineral
glasses.